JP2010265246A - Composition including compound having both nco group and polymerizable c=c double bond - Google Patents
Composition including compound having both nco group and polymerizable c=c double bond Download PDFInfo
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- JP2010265246A JP2010265246A JP2009120219A JP2009120219A JP2010265246A JP 2010265246 A JP2010265246 A JP 2010265246A JP 2009120219 A JP2009120219 A JP 2009120219A JP 2009120219 A JP2009120219 A JP 2009120219A JP 2010265246 A JP2010265246 A JP 2010265246A
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 46
- 239000000203 mixture Substances 0.000 title claims abstract description 37
- 125000000962 organic group Chemical group 0.000 claims abstract description 29
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 18
- 229920005862 polyol Polymers 0.000 claims description 13
- 239000000853 adhesive Substances 0.000 claims description 11
- 230000001070 adhesive effect Effects 0.000 claims description 11
- 150000003077 polyols Chemical class 0.000 claims description 10
- 239000000976 ink Substances 0.000 claims description 8
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000003973 paint Substances 0.000 claims description 7
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 3
- 125000004185 ester group Chemical group 0.000 claims description 3
- 125000001033 ether group Chemical group 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 239000000178 monomer Substances 0.000 abstract description 8
- 125000005442 diisocyanate group Chemical group 0.000 abstract description 7
- 125000000524 functional group Chemical group 0.000 abstract description 6
- 238000003860 storage Methods 0.000 abstract description 6
- 231100000331 toxic Toxicity 0.000 abstract description 4
- 230000002588 toxic effect Effects 0.000 abstract description 4
- 239000011248 coating agent Substances 0.000 description 18
- 238000000576 coating method Methods 0.000 description 16
- -1 ester compounds Chemical class 0.000 description 8
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 4
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 238000001879 gelation Methods 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- RXYPXQSKLGGKOL-UHFFFAOYSA-N 1,4-dimethylpiperazine Chemical compound CN1CCN(C)CC1 RXYPXQSKLGGKOL-UHFFFAOYSA-N 0.000 description 2
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical compound CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 description 2
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 description 2
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 2
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- YXDWGOZSEQBARM-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone;2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1.C=1C=CC=CC=1C(=O)C1(O)CCCCC1 YXDWGOZSEQBARM-UHFFFAOYSA-N 0.000 description 1
- RRUBVRPYWUYCPG-UHFFFAOYSA-N (2-hydroxy-3-phenoxypropyl) prop-2-enoate;(2-hydroxy-3-prop-2-enoyloxypropyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(O)COC(=O)C=C.C=CC(=O)OCC(O)COC1=CC=CC=C1 RRUBVRPYWUYCPG-UHFFFAOYSA-N 0.000 description 1
- DDKMFQGAZVMXQV-UHFFFAOYSA-N (3-chloro-2-hydroxypropyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(O)CCl DDKMFQGAZVMXQV-UHFFFAOYSA-N 0.000 description 1
- BWZAUXRKSMJLMH-UHFFFAOYSA-N 1,1-diethoxyethylbenzene Chemical compound CCOC(C)(OCC)C1=CC=CC=C1 BWZAUXRKSMJLMH-UHFFFAOYSA-N 0.000 description 1
- GJZFGDYLJLCGHT-UHFFFAOYSA-N 1,2-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=C(CC)C(CC)=CC=C3SC2=C1 GJZFGDYLJLCGHT-UHFFFAOYSA-N 0.000 description 1
- UYEDESPZQLZMCL-UHFFFAOYSA-N 1,2-dimethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=C(C)C(C)=CC=C3SC2=C1 UYEDESPZQLZMCL-UHFFFAOYSA-N 0.000 description 1
- YNSNJGRCQCDRDM-UHFFFAOYSA-N 1-chlorothioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2Cl YNSNJGRCQCDRDM-UHFFFAOYSA-N 0.000 description 1
- CTOHEPRICOKHIV-UHFFFAOYSA-N 1-dodecylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2CCCCCCCCCCCC CTOHEPRICOKHIV-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- RWXMAAYKJDQVTF-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethyl prop-2-enoate Chemical compound OCCOCCOC(=O)C=C RWXMAAYKJDQVTF-UHFFFAOYSA-N 0.000 description 1
- FDSUVTROAWLVJA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)COCC(CO)(CO)CO FDSUVTROAWLVJA-UHFFFAOYSA-N 0.000 description 1
- WVRHNZGZWMKMNE-UHFFFAOYSA-N 2-hydroxy-1-[2-(2-methylpropyl)phenyl]-2-phenylethanone Chemical compound CC(C)CC1=CC=CC=C1C(=O)C(O)C1=CC=CC=C1 WVRHNZGZWMKMNE-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- NACPTFCBIGBTSJ-UHFFFAOYSA-N 2-hydroxy-2-phenyl-1-(2-propan-2-ylphenyl)ethanone Chemical compound CC(C)C1=CC=CC=C1C(=O)C(O)C1=CC=CC=C1 NACPTFCBIGBTSJ-UHFFFAOYSA-N 0.000 description 1
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 1
- HMBNQNDUEFFFNZ-UHFFFAOYSA-N 4-ethenoxybutan-1-ol Chemical compound OCCCCOC=C HMBNQNDUEFFFNZ-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- XQBCVRSTVUHIGH-UHFFFAOYSA-L [dodecanoyloxy(dioctyl)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCC XQBCVRSTVUHIGH-UHFFFAOYSA-L 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000007701 flash-distillation Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- ZMHZSHHZIKJFIR-UHFFFAOYSA-N octyltin Chemical compound CCCCCCCC[Sn] ZMHZSHHZIKJFIR-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- IFNXAMCERSVZCV-UHFFFAOYSA-L zinc;2-ethylhexanoate Chemical compound [Zn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O IFNXAMCERSVZCV-UHFFFAOYSA-L 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
本発明は、ＮＣＯ基と重合性Ｃ＝Ｃ二重結合を共に有する化合物を含む組成物および該ＮＣＯ基と重合性Ｃ＝Ｃ二重結合を共に有する化合物を含む組成物を用いたＵＶ硬化型塗料、ＵＶ硬化型粘・接着剤、ＵＶ硬化型インキ、ＵＶ硬化型ハードコート剤等に関する。 The present invention relates to a composition comprising a compound having both an NCO group and a polymerizable C═C double bond, and a UV curable type using the composition comprising a compound having both the NCO group and a polymerizable C═C double bond. The present invention relates to paints, UV curable adhesives, UV curable inks, UV curable hard coating agents, and the like.
これまでに、ジイソシアネートモノマーと水酸基及び重合性Ｃ＝Ｃ二重結合を有する化合物から得られる、ＮＣＯ基と重合性Ｃ＝Ｃ二重結合を共に有する化合物を含む組成物は知られている（例えば、特許文献１及び特許文献２参照）。 So far, compositions comprising compounds having both an NCO group and a polymerizable C═C double bond obtained from a compound having a diisocyanate monomer and a hydroxyl group and a polymerizable C═C double bond are known (eg, Patent Document 1 and Patent Document 2).
しかしながら、上記特許文献１で開示されている、ＮＣＯ基と重合性Ｃ＝Ｃ二重結合を共に有する化合物を含む組成物は、未反応のジイソシアネートモノマーが残存し、その毒性が高く、また、ＮＣＯ基と反応可能な官能基を２つ以上有する主剤と配合すると、主剤の分子間で架橋反応が起こり、増粘又はゲル化するため、貯蔵安定性が良好ではない。 However, the composition containing a compound having both an NCO group and a polymerizable C═C double bond disclosed in Patent Document 1 has an unreacted diisocyanate monomer, and is highly toxic. When blended with a main agent having two or more functional groups capable of reacting with a group, a cross-linking reaction occurs between the molecules of the main agent, resulting in thickening or gelation, so that the storage stability is not good.
また、上記特許文献２では、ジイソシアネートモノマーと水酸基及び重合性Ｃ＝Ｃ二重結合を有する化合物とを、ジイソシアネートモノマー過剰下で反応させた後、過剰に残存するモノマーをフラッシュ蒸留によって分離することで、ＮＣＯ基と重合性Ｃ＝Ｃ二重結合を共に有する化合物を製造することは可能であるが、特殊な設備が必要であることに加えて、熱変性する可能性がある。 Moreover, in the said patent document 2, after making the diisocyanate monomer, the compound which has a hydroxyl group and a polymeric C = C double bond react under diisocyanate monomer excess, the monomer which remains excessively is isolate | separated by flash distillation. Although it is possible to produce a compound having both an NCO group and a polymerizable C═C double bond, in addition to the need for special equipment, there is a possibility of thermal denaturation.
そこで、本発明では、毒性の高い未反応ジイソシアネートモノマーを実質的に含まず、ＮＣＯ基と反応可能な官能基を２つ以上有する主剤と配合した場合でも、増粘しにくいもしくはゲル化しない、つまり、貯蔵安定性が良好であり、さらには、ＵＶ硬化した塗膜の硬度と可とう性のバランスが良好な優れた性能を示す、ＮＣＯ基と重合性Ｃ＝Ｃ二重結合を共に有する化合物を含む組成物を提供することを目的とする。 Therefore, in the present invention, even when blended with a main agent having substantially two or more functional groups capable of reacting with an NCO group substantially free of highly toxic unreacted diisocyanate monomer, it is difficult to thicken or gel. A compound having both an NCO group and a polymerizable C═C double bond, which has excellent storage stability and excellent performance with a good balance between hardness and flexibility of a UV-cured coating film. The object is to provide a composition comprising.
本発明者は、前記課題を解決するため検討を進め、１分子中にＮＣＯ基及び重合性Ｃ＝Ｃ二重結合を共に有する有機基を有する成分（Ａ）と、１分子中に重合性Ｃ＝Ｃ二重結合を有する有機基を２個有する成分（Ｂ）とが特定の組成範囲である組成物が、ＵＶ硬化型塗料、ＵＶ硬化型粘・接着剤、ＵＶ硬化型インキ、ＵＶ硬化型ハードコート剤等の分野で硬度と可とう性のバランスが良好な優れた性能を発揮することを見出し、本発明をなすに至った。 The present inventor has proceeded with studies to solve the above problems, and the component (A) having an organic group having both an NCO group and a polymerizable C═C double bond in one molecule, and a polymerizable C in one molecule. A composition in which the component (B) having two organic groups having a C double bond is in a specific composition range is a UV curable paint, UV curable adhesive, UV curable ink, UV curable ink In the field of hard coating agents and the like, it was found that excellent performance with a good balance between hardness and flexibility was achieved, and the present invention was made.
すなわち、本発明は、
［１］下記、一般式（１）において、
ＸがＮＣＯ基であって、Ｙが重合性Ｃ＝Ｃ二重結合を含む有機基であるか、又はＸが重合性Ｃ＝Ｃ二重結合を含む有機基であって、ＹがＮＣＯ基である化合物（Ａ成分）が２４〜６５ｗｔ％、Ｘ、Ｙがいずれも重合性Ｃ＝Ｃ二重結合を含む有機基である化合物（Ｂ成分）が３４〜７５ｗｔ％、Ｘ、ＹがいずれもＮＣＯ基である化合物（Ｃ成分）が０．０１〜２ｗｔ％の組成を有する、ＮＣＯ基と重合性Ｃ＝Ｃ二重結合を共に有する化合物を含む組成物、
［２］重合性Ｃ＝Ｃ二重結合を含む有機基が下記一般式（２）又は（３）で示される、上記［１］に記載の組成物、
（式中、Ｒ１、Ｒ２はそれぞれＣＨ３又はＨを示し、Ｒ３は任意に分岐鎖、エステル基、エーテル基、カルボニル基を有していてもよい炭素数２〜３０の２価の有機基を示す。）
［３］重合性Ｃ＝Ｃ二重結合を含む有機基が下記式（４）で示される、上記［１］に記載の組成物、
［４］下記、一般式（１）において、
ＸがＮＣＯ基であって、Ｙが重合性Ｃ＝Ｃ二重結合を含む有機基であるか、又はＸが重合性Ｃ＝Ｃ二重結合を含む有機基であって、ＹがＮＣＯ基である化合物（Ａ成分）が２４〜６５ｗｔ％、Ｘ、Ｙがいずれも重合性Ｃ＝Ｃ二重結合を含む有機基である化合物（Ｂ成分）が３４〜７５ｗｔ％、Ｘ、ＹがいずれもＮＣＯ基である化合物（Ｃ成分）が０．０１〜２ｗｔ％の組成を有する、ＮＣＯ基と重合性Ｃ＝Ｃ二重結合を共に有する化合物を含む組成物の製造方法であって、
イソホロンジイソシアネート（ＩＰＤＩ）と、１分子中に水酸基及び重合性Ｃ＝Ｃ二重結合を有する化合物とを、ＮＣＯ／ＯＨ当量比＝１．２〜１．６の範囲で反応させて製造することを特徴とする、前記方法、
［５］（ａ）上記［１］又は［２］に記載の組成物と、
（ｂ）ＯＨ基を２つ以上有するポリオール
とを、（ａ）のＮＣＯ基と（ｂ）のＯＨ基の当量比が１以下の範囲となるように反応して得られる、ＵＶ硬化型塗料、ＵＶ硬化型粘・接着剤、ＵＶ硬化型インキ、又はＵＶ硬化型ハードコート剤、等に関するものである。
That is, the present invention
[1] In the following general formula (1),
X is an NCO group and Y is an organic group containing a polymerizable C═C double bond, or X is an organic group containing a polymerizable C═C double bond, and Y is an NCO group A compound (component A) is 24 to 65 wt%, X and Y are both organic groups containing a polymerizable C═C double bond, and a compound (component B) is 34 to 75 wt%, and X and Y are both NCO. A composition comprising a compound having both an NCO group and a polymerizable C═C double bond, wherein the compound (C component) as a group has a composition of 0.01 to 2 wt%;
[2] The composition according to [1] above, wherein the organic group containing a polymerizable C═C double bond is represented by the following general formula (2) or (3):
(In the formula, R 1 and R 2 each represent CH 3 or H, and R 3 is a divalent C 2-30 optionally having a branched chain, an ester group, an ether group, or a carbonyl group. Indicates an organic group.)
[3] The composition according to [1], wherein the organic group containing a polymerizable C═C double bond is represented by the following formula (4):
[4] In the following general formula (1),
X is an NCO group and Y is an organic group containing a polymerizable C═C double bond, or X is an organic group containing a polymerizable C═C double bond, and Y is an NCO group A compound (component A) is 24 to 65 wt%, X and Y are both organic groups containing a polymerizable C═C double bond, and a compound (component B) is 34 to 75 wt%, and X and Y are both NCO. A method for producing a composition comprising a compound having an NCO group and a polymerizable C═C double bond, wherein the compound (C component) as a group has a composition of 0.01 to 2 wt%,
It is produced by reacting isophorone diisocyanate (IPDI) with a compound having a hydroxyl group and a polymerizable C═C double bond in one molecule in a range of NCO / OH equivalent ratio = 1.2 to 1.6. Said method, characterized by
[5] (a) the composition according to [1] or [2] above;
(B) a UV curable paint obtained by reacting a polyol having two or more OH groups with an equivalent ratio of the NCO group of (a) and the OH group of (b) being 1 or less, The present invention relates to a UV curable adhesive / UV adhesive, a UV curable ink, or a UV curable hard coat agent.
本発明のＮＣＯ基と重合性Ｃ＝Ｃ二重結合を共に有する化合物を含む組成物は、毒性の高い未反応ジイソシアネートモノマーを実質的に含まず、ＮＣＯ基と反応可能な官能基を２つ以上有する主剤（ポリオール等）とを配合した場合でも、増粘しにくい又はゲル化しない、つまり、貯蔵安定性が良好であり、さらには、ＵＶ硬化した塗膜の硬度と可とう性のバランスが良好な優れた性能を示す効果を有する。 The composition containing the NCO group of the present invention and a compound having both a polymerizable C═C double bond is substantially free of highly toxic unreacted diisocyanate monomer and has two or more functional groups capable of reacting with the NCO group. Even when blended with a main ingredient (polyol, etc.), it is difficult to thicken or gel, that is, the storage stability is good, and the balance between the hardness and flexibility of the UV cured coating is good It has the effect of exhibiting excellent performance.
本発明について、以下具体的に説明する。 The present invention will be specifically described below.
本発明のＮＣＯ基と重合性Ｃ＝Ｃ二重結合を共に有する化合物を含む組成物の成分割合としては通常、上記一般式（１）において、ＸがＮＣＯ基であって、Ｙが重合性Ｃ＝Ｃ二重結合を含む有機基であるか、又はＸが重合性Ｃ＝Ｃ二重結合を含む有機基であって、ＹがＮＣＯ基である化合物（Ａ成分）を２４〜６５ｗｔ％、Ｘ、Ｙがいずれも重合性Ｃ＝Ｃ二重結合を含む有機基である化合物（Ｂ成分）を３４〜７５ｗｔ％、及びＸ、ＹがいずれもＮＣＯ基である化合物（Ｃ成分）を０．０１〜２ｗｔ％であり、好ましくは、Ａ成分：２９〜６０ｗｔ％、Ｂ成分：３９〜７０ｗｔ％、Ｃ成分：０．０１〜１ｗｔ％の成分割合を達成することで、該組成物とＯＨ基を含有するポリオール（主剤）とを配合した場合でも、得られた組成物は増粘しにくい又はゲル化しない、つまり、貯蔵安定性が良好であり、さらには、ＵＶ硬化した塗膜の硬度と可とう性のバランスが良好な優れた性能を示す。 The component ratio of the composition containing a compound having both an NCO group and a polymerizable C = C double bond of the present invention is usually that in the general formula (1), X is an NCO group, and Y is a polymerizable C. = An organic group containing a C double bond, or X is an organic group containing a polymerizable C = C double bond and Y is an NCO group (component A) in an amount of 24 to 65 wt%, X , Y is an organic group containing a polymerizable C═C double bond (component B) 34 to 75 wt%, and X and Y are both NCO groups (C component) 0.01 ˜2 wt%, preferably, by achieving the component ratio of A component: 29-60 wt%, B component: 39-70 wt%, C component: 0.01-1 wt%, Even when blended with the contained polyol (main agent), the resulting composition is thickened. Not have or gelled, i.e., have good storage stability, and further, the balance of hardness and flexibility of the UV cured coating exhibits excellent excellent performance.
重合性Ｃ＝Ｃ二重結合を含む有機基として、好ましくは上記の一般式（２）又は（３）で示される有機基であることが好ましい。一般式（２）及び（３）中のＲ１、Ｒ２は、それぞれＣＨ３又はＨであることが好ましく、Ｈであることがさらに好ましい。また、一般式（２）及び（３）中のＲ３はＣＨ２、Ｃ２Ｈ４、Ｃ３Ｈ６、Ｃ４Ｈ８等の分岐鎖、エステル基、エーテル基、カルボニル基を有してもよい炭素数２〜３０の２価の有機基であることが好ましく、Ｃ３Ｈ６であることが更に好ましい。 The organic group containing a polymerizable C═C double bond is preferably an organic group represented by the above general formula (2) or (3). R 1 and R 2 in the general formulas (2) and (3) are each preferably CH 3 or H, and more preferably H. R 3 in the general formulas (2) and (3) has a branched chain such as CH 2 , C 2 H 4 , C 3 H 6 , C 4 H 8 , an ester group, an ether group, and a carbonyl group. It is preferably a C 2-30 divalent organic group, more preferably C 3 H 6 .
本発明のＮＣＯ基と重合性Ｃ＝Ｃ二重結合を共に有する化合物を含む組成物は、イソホロンジイソシアネート（ＩＰＤＩ）と、水酸基及び重合性Ｃ＝Ｃ二重結合を有する化合物とを、配合比（ＮＣＯ／ＯＨ当量比）：１．２〜１．６で反応させることにより、製造可能であるが、特に限定されない。 The composition containing a compound having both an NCO group and a polymerizable C═C double bond of the present invention comprises a compounding ratio of isophorone diisocyanate (IPDI) and a compound having a hydroxyl group and a polymerizable C═C double bond ( NCO / OH equivalent ratio): It can be produced by reacting at 1.2 to 1.6, but is not particularly limited.
前記Ａ成分、Ｂ成分及びＣ成分を含む組成物の原料である、水酸基及び重合性Ｃ＝Ｃ二重結合を有する化合物としては、例えば、２−ヒドロキシエチルアクリレート（２−ＨＥＡ）、２−ヒドロキシプロピルアクリレート（２−ＨＰＡ）、２−ヒドロキシエチルメタクリレート（２−ＨＥＭＡ）、２−ヒドロキシプロピルメタクリレート（２−ＨＰＭＡ）、４−ヒドロキシブチルアクリレート（４−ＨＢＡ）、２−ヒドロキシ−３−フェノキシプロピルアクリレート、２−ヒドロキシ−３−アクリロイロキシプロピルメタクリレート、３−クロロ−２−ヒドロキシプロピルメタクリレート、ジエチレングリコールアクリレート、ポリエチレングリコールアクリレート、ポリプロピレングリコールアクリレート、ペンタエリスリトールトリアクリレート、ジペンタエリスリトールペンタアクリレート、ヒドロキシブチルビニルエーテル、及び上記の水酸基及び重合性Ｃ＝Ｃ二重結合を有する化合物とε−カプロラクトンとの付加物等が挙げられ、これらから選ばれる少なくとも１種が用いられる。 Examples of the compound having a hydroxyl group and a polymerizable C═C double bond as a raw material of the composition containing the A component, the B component, and the C component include 2-hydroxyethyl acrylate (2-HEA), 2-hydroxy Propyl acrylate (2-HPA), 2-hydroxyethyl methacrylate (2-HEMA), 2-hydroxypropyl methacrylate (2-HPMA), 4-hydroxybutyl acrylate (4-HBA), 2-hydroxy-3-phenoxypropyl acrylate 2-hydroxy-3-acryloyloxypropyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol acrylate, polyethylene glycol acrylate, polypropylene glycol acrylate, pentaerythritol triac Rate, dipentaerythritol pentaacrylate, hydroxybutyl vinyl ether, and adducts of the above-mentioned hydroxyl group and a compound having a polymerizable C = C double bond and ε-caprolactone, and at least one selected from these is used. It is done.
イソホロンジイソシアネート（ＩＰＤＩ）と、水酸基及び重合性Ｃ＝Ｃ二重結合を有する化合物との反応温度としては、原料の種類、溶媒の種類、その他の条件により必ずしも一定しないが、通常は３０〜８０℃、好ましくは、５０〜７０℃である。 The reaction temperature between isophorone diisocyanate (IPDI) and a compound having a hydroxyl group and a polymerizable C═C double bond is not necessarily constant depending on the type of raw material, the type of solvent, and other conditions, but usually 30 to 80 ° C. Preferably, it is 50-70 degreeC.
前記反応の反応促進用の触媒としては、ジブチルスズジラウレート、ジオクチルスズジラウレート、２−エチルヘキサン酸スズ、２−エチルヘキサン酸亜鉛、コバルト塩、等の金属塩、トリエチルアミン、ピリジン、メチルピリジン、ベンジルジメチルアミン、Ｎ，Ｎ−ジメチルシクロヘキシルアミン、Ｎ−メチルピペリジン、ペンタメチルジエチレントリアミン、Ｎ，Ｎ’−エンドエチレンピペラジン、及びＮ，Ｎ’−ジメチルピペラジンのような３級アミン類等が挙げられる。その添加量は、反応物の樹脂１００重量部に対して、０．００５〜０．１重量部が好ましい。 Examples of the catalyst for promoting the reaction include metal salts such as dibutyltin dilaurate, dioctyltin dilaurate, tin 2-ethylhexanoate, zinc 2-ethylhexanoate, cobalt salt, triethylamine, pyridine, methylpyridine, benzyldimethylamine , Tertiary amines such as N, N-dimethylcyclohexylamine, N-methylpiperidine, pentamethyldiethylenetriamine, N, N′-endoethylenepiperazine, and N, N′-dimethylpiperazine. The addition amount is preferably 0.005 to 0.1 parts by weight with respect to 100 parts by weight of the resin of the reaction product.
本発明のＮＣＯ基と重合性Ｃ＝Ｃ二重結合を共に有する化合物を含む組成物、水酸基を２つ以上有するポリオール、ＵＶ硬化型塗料、ＵＶ硬化型粘・接着剤、ＵＶ硬化型インキ、ＵＶ硬化型ハードコート剤等はいずれも、有機溶剤で希釈することができる。この場合、有機溶剤は、水酸基及びＮＣＯ基と反応する官能基を有していない方が好ましい。また、有機溶剤は本発明で用いるＮＣＯ基と重合性Ｃ＝Ｃ二重結合を共に有する化合物を含む組成物、ＯＨ基を２つ以上有するポリオール、ＵＶ硬化型塗料、ＵＶ硬化型粘・接着剤、ＵＶ硬化型インキ、ＵＶ硬化型ハードコート剤等と相溶する方が好ましい。このような有機溶剤として、一般に塗料溶剤として用いられているエステル化合物や、エーテル化合物、ケトン化合物、芳香族化合物、エチレングリコールジアルキルエーテル系の化合物、ポリエチレングリコールジカルボキシレート系の化合物、炭化水素系溶剤、芳香族系溶剤などが挙げられる。 Composition comprising a compound having both an NCO group and a polymerizable C = C double bond of the present invention, a polyol having two or more hydroxyl groups, a UV curable paint, a UV curable adhesive / adhesive, a UV curable ink, UV Any of the curable hard coat agent and the like can be diluted with an organic solvent. In this case, the organic solvent preferably does not have a functional group that reacts with a hydroxyl group and an NCO group. Further, the organic solvent is a composition containing a compound having both an NCO group and a polymerizable C═C double bond used in the present invention, a polyol having two or more OH groups, a UV curable paint, and a UV curable adhesive / adhesive. It is preferable to be compatible with UV curable ink, UV curable hard coat agent and the like. As such organic solvents, ester compounds, ether compounds, ketone compounds, aromatic compounds, ethylene glycol dialkyl ether compounds, polyethylene glycol dicarboxylate compounds, hydrocarbon solvents generally used as paint solvents And aromatic solvents.
本発明の水酸基を２つ以上有するポリオールとしては、アクリルポリオール類、ポリエステルポリオール類、ポリエーテルポリオール類、脂肪族炭化水素ポリオール類、及びエポキシ樹脂類等が挙げられる。 Examples of the polyol having two or more hydroxyl groups of the present invention include acrylic polyols, polyester polyols, polyether polyols, aliphatic hydrocarbon polyols, and epoxy resins.
本発明の（ａ）ＮＣＯ基と重合性Ｃ＝Ｃ二重結合を共に有する化合物を含む組成物を調製する際のＮＣＯ基と、（ｂ）ＯＨ基を２つ以上有するポリオールのＯＨ基の配合比（ＮＣＯ／ＯＨ当量比）は１以下、好ましくは、０．５以上１以下を達成することで、主剤への二重結合の導入割合を上げることができる。 Formulation of (a) an NCO group and (b) an OH group of a polyol having two or more OH groups when preparing a composition containing a compound having both an NCO group and a polymerizable C═C double bond of the present invention By achieving the ratio (NCO / OH equivalent ratio) of 1 or less, preferably 0.5 or more and 1 or less, the introduction ratio of double bonds to the main agent can be increased.
本発明の光重合開始剤としては、ベンゾイン、イソプロピルベンゾインエーテル、イソブチルベンゾインエーテル、ベンゾフェノン、ミヒラーケトン、クロロチオキサントン、ドデシルチオキサントン、ジメチルチオキサントン、ジエチルチオキサントン、アセトフェノンジエチルケタール、ベンジルジメチルケタール、１−ヒドロキシシクロヘキシルフェニルケトン、２−ヒドロキシ−２−メチル−１−フェニルプロパン−１−オン等が挙げられ、これらから選ばれる少なくとも１種が用いられる。好ましくは、ベンジルジメチルケタール、１−ヒドロキシシクロヘキシルフェニルケトン、２−ヒドロキシ−２−メチル−１−フェニルプロパン−１−オンが用いられる。その添加量は、通常、樹脂１００重量部に対して、０．０１〜５重量部、好ましくは０．１〜３重量部である。 Examples of the photopolymerization initiator of the present invention include benzoin, isopropyl benzoin ether, isobutyl benzoin ether, benzophenone, Michler ketone, chlorothioxanthone, dodecyl thioxanthone, dimethylthioxanthone, diethylthioxanthone, acetophenone diethyl ketal, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone 2-hydroxy-2-methyl-1-phenylpropan-1-one and the like, and at least one selected from these is used. Preferably, benzyl dimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one is used. The addition amount is usually 0.01 to 5 parts by weight, preferably 0.1 to 3 parts by weight, with respect to 100 parts by weight of the resin.
ＵＶ照射を行なう時の光源としては、高圧水銀灯、超高圧水銀灯カーボンアーク灯、キセノン灯、メタルハライドランプ、ケミカルランプ、ブラックライト等が用いられる。高圧水銀ランプの場合は、例えば５〜３０００ｍＪ／ｃｍ２、好ましくは、１０〜１０００ｍＪ／ｃｍ２の条件で行なわれる。照射時間は、光源の種類、光源と塗布面との距離、塗工厚、その他の条件によっても異なるが、通常は数秒〜数十秒、場合によっては数分の１秒でもよい。 As a light source for performing UV irradiation, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a xenon lamp, a metal halide lamp, a chemical lamp, a black light, or the like is used. In the case of a high-pressure mercury lamp, for example, it is performed under conditions of 5 to 3000 mJ / cm 2 , preferably 10 to 1000 mJ / cm 2 . The irradiation time varies depending on the type of light source, the distance between the light source and the coating surface, the coating thickness, and other conditions, but it may be usually from several seconds to several tens of seconds, and in some cases, may be a fraction of a second.
本発明を実施例に基づいて説明する。なお、実施例で得られた組成物及び塗膜の特性は下記の方法により求めた。 The present invention will be described based on examples. In addition, the characteristic of the composition obtained by the Example and a coating film was calculated | required with the following method.
組成物中のＡ成分、Ｂ成分及びＣ成分のそれぞれの含有量は、示差屈折率計検出によるゲルパーミエーションクロマトグラフィ（ＧＰＣ）によって測定した各成分ピークの面積百分率にて求められる。 Each content of A component, B component, and C component in a composition is calculated | required by the area percentage of each component peak measured by the gel permeation chromatography (GPC) by a differential refractometer detection.
ＮＣＯ％は、ＮＣＯ基を過剰の２Ｎアミンで中和した後、１Ｎ塩酸による逆滴定によって測定した。 NCO% was measured by back titration with 1N hydrochloric acid after neutralizing the NCO groups with excess 2N amine.
粘度は、Ｅ型粘度計（東機産業株式会社のＲＥ−８５Ｒ）を用いて、２５℃で測定した。なお、標準ローター（１°３４’×Ｒ２４）を用いた。回転数は、以下の通り。
１００ｒ．ｐ．ｍ． （１２８ｍＰａ・ｓ未満の場合）
５０ｒ．ｐ．ｍ． （１２８ｍＰａ・ｓ〜２５６ｍＰａ・ｓの場合）
２０ｒ．ｐ．ｍ． （２５６ｍＰａ・ｓ〜６４０ｍＰａ・ｓの場合）
１０ｒ．ｐ．ｍ． （６４０ｍＰａ・ｓ〜１２８０ｍＰａ・ｓの場合）
５ｒ．ｐ．ｍ． （１２８０ｍＰａ・ｓ〜２５６０ｍＰａ・ｓの場合）
ＵＶ照射は、小型ＵＶ照射装置（オーク製造社のハンディＵＶ−３００）を用いた。
The viscosity was measured at 25 ° C. using an E-type viscometer (RE-85R manufactured by Toki Sangyo Co., Ltd.). A standard rotor (1 ° 34 ′ × R24) was used. The number of revolutions is as follows.
100r. p. m. (If less than 128 mPa · s)
50r. p. m. (In the case of 128 mPa · s to 256 mPa · s)
20r. p. m. (In the case of 256 mPa · s to 640 mPa · s)
10r. p. m. (In the case of 640 mPa · s to 1280 mPa · s)
5r. p. m. (In the case of 1280 mPa · s to 2560 mPa · s)
For UV irradiation, a small UV irradiation apparatus (Oak Manufacturing Handy UV-300) was used.
ＵＶ硬化塗膜の物性について、硬度はケーニッヒ硬度計（ＢＹＫ Ｇａｒｄｅｒ社のＰｅｎｄｕｌｕｍ ｈａｒｄｎｅｓｓ ｔｅｓｔｅｒ）を用いて、耐衝撃性はＪＩＳ−Ｋ−５６００−５−３（デュポン式）に準じて測定した。
［実施例１］
４口フラスコに、ＮＣＯ／ＯＨ当量比＝１．４３となるように、ＩＰＤＩ（商品名：ＶＥＳＴＡＮＡＴ ＩＰＤＩ、エボニックデグサ製）を４４．１重量部、２―ヒドロキシプロピルアクリレート（２−ＨＰＡ、日本触媒製）を３５．９重量部、酢酸ｎ−ブチルを２０．０重量部、ＢＨＴを０．２重量部で仕込み、４０℃へ昇温する。反応熱に注意しながら、オクチルスズ系触媒（商品名：Ｕ−８１０、日東化成製）を添加していき、発熱がなくなった時点で６０℃へ昇温した。ＮＣＯ％が計算値付近（５．０％）になったところで、反応を終了し、ウレタンアクリレートオリゴマー１を合成した。以下、Ｕ１とする。
Regarding the physical properties of the UV-cured coating film, the hardness was measured according to JIS-K-5600-5-3 (DuPont type) using a König hardness tester (Pendulum hardness tester of BYK Garder).
[Example 1]
In a 4-neck flask, 44.1 parts by weight of IPDI (trade name: VESTANAT IPDI, manufactured by Evonik Degussa) so that the NCO / OH equivalent ratio = 1.43, 2-hydroxypropyl acrylate (2-HPA, Nippon Shokubai) Made of 35.9 parts by weight, n-butyl acetate 20.0 parts by weight, and BHT 0.2 parts by weight, and the temperature is raised to 40 ° C. While paying attention to the heat of reaction, an octyltin-based catalyst (trade name: U-810, manufactured by Nitto Kasei) was added, and the temperature was raised to 60 ° C. when no heat was generated. When NCO% was close to the calculated value (5.0%), the reaction was terminated and urethane acrylate oligomer 1 was synthesized. Hereinafter, it is referred to as U1.
得られたＵ１は、ＮＣＯ含有量：５．０％、粘度：３００ｍＰａ・ｓであり、ＧＰＣ測定結果から、ＮＣＯ基を１つ有しＮＣＯ基の１つがアクリレート化された化合物（片末端アクリレート体：成分（Ａ））の含有量：４９％、ＮＣＯ基を有さずＮＣＯ基の２つがアクリレート化された化合物（両末端アクリレート体：成分（Ｂ））の含有量：５１％、未反応ＩＰＤＩ（成分（Ｃ））の含有量：１％未満であった。
［実施例２］
表１に示すように、ＮＣＯ／ＯＨ当量比＝１．２５とした以外は、実施例１と同様にして、ウレタンアクリレートオリゴマー２を合成した。以下、Ｕ２とする。なお、分析値については表２に示す。
［実施例３］
表１に示すように、２−ＨＰＡを２−ヒドロキシエチルアクリレート（２−ＨＥＡ、東亜合成製）にした以外は、実施例１と同様にして、ウレタンアクリレートオリゴマー３を合成した。以下、Ｕ３とする。なお、分析値については表２に示す。
［実施例４］
表１に示すように、２−ＨＰＡを２−ヒドロキシエチルメタクリレート（２−ＨＥＭＡ、日本触媒製）にした以外は、実施例１と同様にして、ウレタンアクリレートオリゴマー４を合成した。以下、Ｕ４とする。なお、分析値については表２に示す。
［比較例１］
表１に示すように、ＮＣＯ／ＯＨ当量比＝２．００とした以外は、実施例１と同様にして、ウレタンアクリレートオリゴマー５を合成した。以下、Ｕ５とする。なお、分析値については表２に示す。
［比較例２］
表１に示すように、ＮＣＯ／ＯＨ当量比＝１．６７とした以外は、実施例１と同様にして、ウレタンアクリレートオリゴマー６を合成した。以下、Ｕ６とする。なお、分析値については表２に示す。
［比較例３］
表１に示すように、ＮＣＯ／ＯＨ当量比＝１．１１とした以外は、実施例１と同様にして、ウレタンアクリレートオリゴマー７を合成した。以下、Ｕ７とする。なお、分析値については表２に示す。
［実施例５］
アクリルポリオール（Ｓｅｔａｌｕｘ１１８４ ＳＳ−５１、Ｎｕｐｌｅｘ製、以下、Ａ１とする。）に対して、Ｕ１をＮＣＯ／ＯＨ当量比＝１、トータル固形分が４０％となるように酢酸ｎ−ブチルで希釈した条件下で、ＮＣＯのピーク（ＩＲ測定）が消失するまで反応させた溶液の外観を観察したところ、ゲル化せずに良好な結果であった（表３）。なお、ゲル化せず：○、ゲル化：×という記号で表す。
The obtained U1 has an NCO content of 5.0% and a viscosity of 300 mPa · s, and from a GPC measurement result, a compound having one NCO group and one acrylated NCO group (one-end acrylate body) : Component (A)) content: 49%, NCO group-free compound with two NCO groups acrylated (both terminal acrylates: component (B)) content: 51%, unreacted IPDI The content of (component (C)) was less than 1%.
[Example 2]
As shown in Table 1, urethane acrylate oligomer 2 was synthesized in the same manner as in Example 1 except that the NCO / OH equivalent ratio was 1.25. Hereinafter, U2. The analysis values are shown in Table 2.
[Example 3]
As shown in Table 1, urethane acrylate oligomer 3 was synthesized in the same manner as in Example 1 except that 2-HPA was changed to 2-hydroxyethyl acrylate (2-HEA, manufactured by Toagosei Co., Ltd.). Hereinafter, it is referred to as U3. The analysis values are shown in Table 2.
[Example 4]
As shown in Table 1, urethane acrylate oligomer 4 was synthesized in the same manner as in Example 1 except that 2-HPA was changed to 2-hydroxyethyl methacrylate (2-HEMA, manufactured by Nippon Shokubai Co., Ltd.). Hereinafter, it is referred to as U4. The analysis values are shown in Table 2.
[Comparative Example 1]
As shown in Table 1, urethane acrylate oligomer 5 was synthesized in the same manner as Example 1 except that the NCO / OH equivalent ratio was 2.00. Hereinafter, it is referred to as U5. The analysis values are shown in Table 2.
[Comparative Example 2]
As shown in Table 1, urethane acrylate oligomer 6 was synthesized in the same manner as in Example 1 except that the NCO / OH equivalent ratio was 1.67. Hereinafter, it is referred to as U6. The analysis values are shown in Table 2.
[Comparative Example 3]
As shown in Table 1, urethane acrylate oligomer 7 was synthesized in the same manner as in Example 1 except that the NCO / OH equivalent ratio was 1.11. Hereinafter, it is referred to as U7. The analysis values are shown in Table 2.
[Example 5]
U1 was diluted with n-butyl acetate so that NCO / OH equivalent ratio = 1 and the total solid content was 40% with respect to acrylic polyol (Setalux 1184 SS-51, manufactured by Nuplex, hereinafter referred to as A1). Below, the appearance of the reacted solution was observed until the NCO peak (IR measurement) disappeared, and it was a good result without gelation (Table 3). In addition, it does not gelatinize: It represents by the code | symbol of (circle) and gelation: x.
さらに、光開始剤（１−ヒドロキシシクロヘキシルフェニルケトン）を２ｗｔ％／固形分となるように配合し、ガラス板・軟鋼板それぞれに塗工した（乾燥膜厚：約４０μｍ）。１００℃のオーブンで５分間、酢酸ｎ−ブチルを揮発後、ＵＶ照射を１分間させて、ＵＶ硬化塗膜を得た。 Furthermore, a photoinitiator (1-hydroxycyclohexyl phenyl ketone) was blended so as to be 2 wt% / solid, and applied to each of a glass plate and a mild steel plate (dry film thickness: about 40 μm). After volatilizing n-butyl acetate in an oven at 100 ° C. for 5 minutes, UV irradiation was performed for 1 minute to obtain a UV cured coating film.
ＵＶ硬化塗膜のケーニッヒ硬度（ガラス板）・耐衝撃性（軟鋼板）を測定した。結果は、表３に示す。なお、ケーニッヒ硬度については、１２１以上：◎（優）、１０１〜１２０：○（良）、１００以下：×（不可）、耐衝撃性については、１／２インチ（撃ち型及び受け台の寸法）＊３００ｇ（おもりの質量）＊３０ｃｍ（おもりの高さ）以上：◎、１／２インチ＊３００ｇ＊１５ｃｍ〜２５ｃｍ：○、１／２インチ＊３００ｇ＊１０ｃｍ以下：×という記号で表す。
［実施例６］
Ｕ１をＵ２とした以外は、実施例５と同様にして、Ａ１と配合後の溶液外観の観察およびＵＶ硬化塗膜物性の評価を行なった。結果は、表３に示す。
［実施例７］
Ｕ１をＵ３とした以外は、実施例５と同様にして、Ａ１と配合後の溶液外観の観察およびＵＶ硬化塗膜物性の評価を行なった。結果は、表３に示す。
［実施例８］
Ｕ１をＵ４とした以外は、実施例５と同様にして、Ａ１と配合後の溶液外観の観察およびＵＶ硬化塗膜物性の評価を行なった。結果は、表３に示す。
［比較例４］
Ｕ１をＵ５とした以外は、実施例５と同様にして、Ａ１と配合後の溶液外観の観察およびＵＶ硬化塗膜物性の評価を行なった。結果は、表３に示す。
［比較例５］
Ｕ１をＵ６とした以外は、実施例５と同様にして、Ａ１と配合後の溶液外観の観察およびＵＶ硬化塗膜物性の評価を行なった。結果は、表３に示す。
［比較例６］
Ｕ１をＵ７とした以外は、実施例５と同様にして、Ａ１と配合後の溶液外観の観察およびＵＶ硬化塗膜物性の評価を行なった。結果は、表３に示す。
The König hardness (glass plate) and impact resistance (soft steel plate) of the UV cured coating film were measured. The results are shown in Table 3. In addition, about Koenig hardness, 121 or more: ◎ (excellent), 101-120: ○ (good), 100 or less: × (impossible), about impact resistance, 1/2 inch (dimensions of shooting mold and cradle) ) * 300 g (mass of weight) * 30 cm (height of weight) or more: ◎, 1/2 inch * 300 g * 15 cm to 25 cm: ◯, 1/2 inch * 300 g * 10 cm or less: Expressed by the symbol x.
[Example 6]
Except that U1 was changed to U2, in the same manner as in Example 5, observation of the appearance of the solution after blending with A1 and evaluation of physical properties of the UV cured coating film were performed. The results are shown in Table 3.
[Example 7]
Except that U1 was changed to U3, in the same manner as in Example 5, observation of the appearance of the solution after blending with A1 and evaluation of physical properties of the UV-cured coating film were performed. The results are shown in Table 3.
[Example 8]
Except that U1 was changed to U4, in the same manner as in Example 5, observation of the appearance of the solution after blending with A1 and evaluation of physical properties of the UV cured coating film were performed. The results are shown in Table 3.
[Comparative Example 4]
Except that U1 was changed to U5, the appearance of the solution after blending with A1 and the evaluation of physical properties of the UV-cured coating film were performed in the same manner as in Example 5. The results are shown in Table 3.
[Comparative Example 5]
Except that U1 was changed to U6, in the same manner as in Example 5, observation of the appearance of the solution after blending with A1 and evaluation of physical properties of the UV cured coating film were performed. The results are shown in Table 3.
[Comparative Example 6]
Except that U1 was changed to U7, in the same manner as in Example 5, observation of the appearance of the solution after blending with A1 and evaluation of physical properties of the UV cured coating film were performed. The results are shown in Table 3.
本発明のＮＣＯ基と重合性Ｃ＝Ｃ二重結合を共に有する化合物を含む組成物は、ＮＣＯ基と反応可能な官能基を２つ以上有する主剤（ポリオール等）と配合した場合でも、増粘しにくい又はゲル化しない、つまり、貯蔵安定性が良好であり、さらには、ＵＶ硬化した塗膜の硬度と可とう性のバランスが良好な優れた性能を示すために、ＵＶ硬化型塗料、ＵＶ硬化型粘・接着剤、ＵＶ硬化型インキ、ＵＶ硬化型ハードコート剤等の分野で好適に利用できる。
The composition containing a compound having both an NCO group and a polymerizable C = C double bond of the present invention has a thickening effect even when blended with a main agent (polyol or the like) having two or more functional groups capable of reacting with the NCO group. In order to exhibit excellent performance that is hard to be gelled or gelled, that is, has good storage stability and a good balance between hardness and flexibility of a UV-cured coating film, It can be suitably used in the fields of curable adhesive / adhesive, UV curable ink, UV curable hard coat agent and the like.
Claims (5)
ＸがＮＣＯ基であって、Ｙが重合性Ｃ＝Ｃ二重結合を含む有機基であるか、又はＸが重合性Ｃ＝Ｃ二重結合を含む有機基であって、ＹがＮＣＯ基である化合物（Ａ成分）が２４〜６５ｗｔ％、Ｘ、Ｙがいずれも重合性Ｃ＝Ｃ二重結合を含む有機基である化合物（Ｂ成分）を３４〜７５ｗｔ％、及びＸ、ＹがいずれもＮＣＯ基である化合物（Ｃ成分）を０．０１〜２ｗｔ％の組成を有する、ＮＣＯ基と重合性Ｃ＝Ｃ二重結合を共に有する化合物を含む組成物。 In the following general formula (1),
X is an NCO group and Y is an organic group containing a polymerizable C═C double bond, or X is an organic group containing a polymerizable C═C double bond, and Y is an NCO group A compound (component A) is 24 to 65 wt%, X and Y are both organic groups containing a polymerizable C═C double bond, and a compound (component B) is 34 to 75 wt%, and X and Y are both A composition comprising a compound having both an NCO group and a polymerizable C═C double bond having a composition of 0.01 to 2 wt% of a compound (component C) that is an NCO group.
（式中、Ｒ１、Ｒ２はそれぞれＣＨ３又はＨを示し、Ｒ３は任意に分岐鎖、エステル基、エーテル基、カルボニル基を有していてもよい炭素数２〜３０の２価の有機基を示す。） The composition according to claim 1, wherein the organic group containing a polymerizable C = C double bond is represented by the following general formula (2) or (3).
(In the formula, R 1 and R 2 each represent CH 3 or H, and R 3 is a divalent C 2-30 optionally having a branched chain, an ester group, an ether group, or a carbonyl group. Indicates an organic group.)
ＸがＮＣＯ基であって、Ｙが重合性Ｃ＝Ｃ二重結合を含む有機基であるか、又はＸが重合性Ｃ＝Ｃ二重結合を含む有機基であって、ＹがＮＣＯ基である化合物（Ａ成分）が２４〜６５ｗｔ％、Ｘ、Ｙがいずれも重合性Ｃ＝Ｃ二重結合を含む有機基である化合物（Ｂ成分）を３４〜７５ｗｔ％、及びＸ、ＹがいずれもＮＣＯ基である化合物（Ｃ成分）を０．０１〜２ｗｔ％の組成を有する、ＮＣＯ基と重合性Ｃ＝Ｃ二重結合を共に有する化合物を含む組成物の製造方法であって、
イソホロンジイソシアネート（ＩＰＤＩ）と、１分子中に水酸基及び重合性Ｃ＝Ｃ二重結合を有する化合物とを、ＮＣＯ／ＯＨ当量比＝１．２〜１．６の範囲で反応させて製造することを特徴とする、前記方法。 In the following general formula (1),
X is an NCO group and Y is an organic group containing a polymerizable C═C double bond, or X is an organic group containing a polymerizable C═C double bond, and Y is an NCO group A compound (component A) is 24 to 65 wt%, X and Y are both organic groups containing a polymerizable C═C double bond, and a compound (component B) is 34 to 75 wt%, and X and Y are both A method for producing a composition comprising a compound having both an NCO group and a polymerizable C═C double bond having a composition of 0.01 to 2 wt% of a compound that is an NCO group (component C),
It is produced by reacting isophorone diisocyanate (IPDI) with a compound having a hydroxyl group and a polymerizable C═C double bond in one molecule in a range of NCO / OH equivalent ratio = 1.2 to 1.6. Said method.
（ｂ）ＯＨ基を２つ以上有するポリオール
とを、（ａ）のＮＣＯ基と（ｂ）のＯＨ基の当量比が１以下の範囲となるように反応して得られる、ＵＶ硬化型塗料、ＵＶ硬化型粘・接着剤、ＵＶ硬化型インキ、又はＵＶ硬化型ハードコート剤。
(A) the composition according to claim 1 or 2, and
(B) a UV curable paint obtained by reacting a polyol having two or more OH groups with an equivalent ratio of the NCO group of (a) and the OH group of (b) being 1 or less, UV curable adhesives, UV curable inks, or UV curable hard coat agents.
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| WO2016118502A1 (en) * | 2015-01-20 | 2016-07-28 | Valspar Sourcing, Inc. | Polymers, coating compositions, coated articles, and methods related thereto |
| JP2017122213A (en) * | 2015-12-21 | 2017-07-13 | エボニック デグサ ゲーエムベーハーＥｖｏｎｉｋ Ｄｅｇｕｓｓａ ＧｍｂＨ | Acrylate-terminated urethane polybutadienes from low-monomer 1:1 monoadducts from reactive olefinic compounds and diisocyanates and hydroxy-terminated polybutadienes for liquid optically clear adhesives (locas) |
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| JP2017122213A (en) * | 2015-12-21 | 2017-07-13 | エボニック デグサ ゲーエムベーハーＥｖｏｎｉｋ Ｄｅｇｕｓｓａ ＧｍｂＨ | Acrylate-terminated urethane polybutadienes from low-monomer 1:1 monoadducts from reactive olefinic compounds and diisocyanates and hydroxy-terminated polybutadienes for liquid optically clear adhesives (locas) |
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